Corrosion resistant coatings containing an amorphous phase

ABSTRACT

The disclosure relates to the forming mineralized coatings on metal surfaces and to methods of forming such coatings. The coating can include a wide range of compounds and normally at least a portion of the coating corresponds to an amorphous phase. The coating and method are particularly useful in providing a corrosion resistant coating or film upon a metallic surface. This aspect of the disclosure involves the formation of a corrosion resistant &#34;mineralized&#34; layer of tailored composition upon a metal substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of U.S. patent application Ser. No. 08/634,215 now abandoned (Attorney Docket No. EL001RH-3), entitled "Corrosion Resistant buffer System for Metal Products" and filed on Apr. 18, 1996 in the names of Robert L. Heimann, et al., which is a continuation in part of U.S. patent application Ser. No. 08/476,271 filed on Jun. 7, 1995, now abandoned, which in turn is a continuation-in-part of U.S. patent application Ser. No. 08/327,438 allowed filed on Oct. 21, 1994, now U.S. Pat. No. 5,714,093. This application is also related to U.S. patent application Ser. No. 08/791,337 pending (Attorney Docket No. EL001RH-4), filed on even date herewith. The disclosure of each of the previously identified patent applications is hereby incorporated by reference.

FIELD OF THE INVENTION

The instant invention relates to the forming coatings on metal containing surfaces and to methods of forming such coatings on a suitable substrate. The coating can include a wide range of compounds and normally at least a portion of the coating corresponds to an amorphous phase. The inventive coating and method are particularly useful in providing a corrosion resistant coating or film upon a metallic surface. This aspect of the invention involves the formation of a corrosion resistant "mineralized" layer of tailored composition upon a metal containing surfaces.

BACKGROUND OF THE INVENTION

The corrosion of steel and other metal containing products continues to be a serious technical problem which has profound effects on the economy. Corrosion causes loss of natural resources, and deteriorates key infrastructure such as roads and buildings. It also causes premature replacement of equipment and parts in industrial facilities, boats and other marine vehicles, automobiles, aircraft, among a wide range of metallic components.

Current industry standards for corrosion prevention center around the use of barrier coatings, sacrificial coatings, alloys containing heavy metals such as chromium, nickel, lead, cadmium, copper, mercury, barium, among other heavy metals. The introduction of these materials into the environment, however, can lead to serious health consequences as well as substantial costs to contain or separate the materials or clean up environmental contamination. Damage associated with corrosion, accordingly, is a continuing problem and better systems for preventing corrosion are still needed.

A more detailed discussion of mineral containing materials can be found in Manual of Mineralogy, by Dana, 21^(st) edition, American Society of Metals, vol. 13, Corrosion in Structures, "Reaction Sequence in Atmospheric Corrosion of Zinc ASTM STP 1239", by W. W. Kirk et al., and Physics and Chemistry of Mineral Surfaces, by Bradly (1996); the disclosure of each of the aforementioned references is hereby incorporated by reference.

Conventional practices for improving protecting metal containing surfaces and imparting improved surface characteristics to metals rely upon compositions and methods which are undesirable as being costly or environmentally unsound.

SUMMARY OF THE INVENTION

The instant invention solves problems associated with conventional practices by providing an improved method and a composition for improving the surface characteristics of a metal containing surface. While the inventive composition is normally compatible with conventional compositions and methods, the inventive composition can obviate the need to employ heavy metals such as chrome and environmentally undesirable solvents.

The present invention in a broad aspect relates to compositions and methods for improving or modifying the surface characteristics of a metal containing surface. In one aspect, the invention involves methods for forming a "mineralized" layer upon the surface of a substrate. One method of forming the mineralized layer comprises delivering precursors of the mineralized layer to the surface of the metal surface via a carrier. The carrier can be a wide range of known compositions such as a film forming composition, lubricants, gel, sealant, adhesive, paint, solvent and waterborne resins, among other conventional compositions for forming coatings or films upon metals. If desired, the carrier can function as a reservoir of precursor materials thereby permitting additional formation of the mineralized layer, e.g., when in the presence of a reservoir a breach in the mineralized layer can be overcome by secondary mineral formation from mineral precursors in the reservoir - a so-called self healing effect. If desired, the carrier can also function as a reservoir of buffer materials, e.g., materials that passivate the pH of the metal surface, which can protect the metal surface by providing an environment in which the metal is resistant to chemical attack. Depending upon the utility of the carrier, the carrier can be removed or remain permanently in contact with the mineralized surface (and at least a portion of the metal surface).

The instant invention provides an improved surface on articles by tailoring the surface chemistry and effecting a new mineralized surface through chemical reaction and interaction. The mineralized surface is formed when precursors are delivered to the surface of a metal or metal coated articles or substrates. In some cases, the carrier includes materials which can function to buffer the surface, as a precursor of the mineralized layer, alter pH, or all of these functions. After providing a proper environment, precursors can interact thereby in situ forming the mineralized layer upon at least a portion of the metal surface. Depending upon the surface environment, the metal or metal coated substrate can contribute donor ions to react and/or interact with delivered precursors thereby forming a relatively thin mineralized layer that is effective in altering and preferably enhance the characteristics of the entire article, e.g., by altering and preferably enhancing the surface characteristics of the article. Consequently, the instant invention permits tailoring a metal containing surface to possess improved corrosion, coating adhesion, chemical resistance, thermal resistance, mechanical abrasion, acid rain resistance, UV resistance, resistance to effects from atomic oxygen and vacuum UV, engineered electrical resistance, among other improved properties. As will be described below in greater detail, at least a portion of the mineralized coating or layer normally corresponds to a novel amorphous phase.

DETAILED DESCRIPTION

The instant invention relates to compositions and methods for forming a mineralized coating or film upon at least a portion of a metal containing surface. By "mineralized" it is meant a composition containing at least one member selected from the group of oxygenated cations and anions wherein at least a portion of the mineral corresponds to an amorphous phase, an inorganic complex oxide crystal and mixtures thereof. Normally, the amorphous phase is the predominate phase component of the mineralized layer and substantially transparent to visible light. By "metal containing surface", "substrate", or "surface" it is meant to refer to a metallic article and any metal containing surface as well as any substrate at least partially coated with a metal layer, film or foil including a non-metallic article having a metal layer. A wide variety of substances can be employed as precursors of the mineralized layer, such as one or more cations of the metals of Groups I, II and III, and the transition metals, of the Periodic Chart of the Elements and one or more of the anions selected from the group consisting of silicates, molybdates, phosphates, zirconates, titanates, tungstates, vandates, permanganate, pertechnetate, chromate, nitrate, carbonates, aluminates, ferrates, mixtures thereof, among others. At least a portion of the resulting mineralized layer having ceramic attributes comprises:

M_(x) M'_(y) M"_(z) (SiO₄)_(t) (Si₂ O₇)_(u) (OH)₂.nH₂ O where M, M' and M" each comprise a cation selected from the group consisting of Group I, II and III metals, and wherein x, y and z each can be any number including zero provided that x, y and z are not all concurrently zero; and t and u each can be any number including zero provided that t and u are not both concurrently zero. The mineralized surface comprises an amorphous phase and an inorganic oxide crystal wherein the amount of oxygen is less than stoichiometric.

The mineralized layer is formed from precursors. By "precursors" it is meant any combination of materials which interact to form the mineralized layer as well as intermediate products that interact further to form the mineralized layer. Examples of precursors include buffers such as silicate buffers and carbonate buffers including sodium hydroxide; silicates such as at least one of sodium, calcium and potassium silicate; silica; cations supplied or delivered to the surface such as at least one of zinc, molybdenium; ions supplied or delivered to the surface such as at least one of oxygen, sulfur or chlorine from the environment surrounding the precursors or surface; compounds which decompose or react to form a precursor or intermediate thereof; mixtures thereof, among others.

The precursors of the mineralized layer are added to any suitable carrier. Examples of suitable carriers include hydrocarbons such as at least one member selected from the group consisting of animal, vegetable, petroleum derived and synthetic oils such as polyalphaolefin (PAO), silicone oil, phosphate esters, fluorinated oils such as KRYTOX (supplied by the DuPont Company). Further examples of suitable carriers comprise at least one member selected from the group consisting of thermoplastic, thermosetting, cross-linked system, mixtures thereof, among others. Specific examples of such carriers include epoxies, acrylics, polyurethanes, silicones, polyesters, alkyds, vinyls, phenolics, fluoropolymers, latexes, mixtures thereof, among others. Depending upon the process conditions, the precursor carrier may be selected from alkylated aromatics, phosphate esters, perfluoroalkylpolyethers, polyesters, olefins, chlorotrifluoroethylene, silahydrocarbons, phosphazenes, dialkylcarbonates, oligomers, polybutenes, and polyphenyl esters, as well as unsaturated polyglycols, silicones, silicate esters, cycloaliphatic hydrocarbons, and dibasic acid esters, e.g., when applying a precursor carrier to an iron containing surface a polyalphaolefin base oil having a kinematic viscosity in the range of about 30-1,400 centistokes at 40° C. can be employed. Other properties to consider when choosing an appropriate polyalphaolefin base oil are molecular weight, molecular branching, thermal stability, and hydrophobicity, depending on the application. The polyalphaolefin base oil can be thickened to a gel with thickeners known to the art of grease manufacturers such as polytetrafluoroethylene or silica. Buffer materials are also suitable as thickeners as long as they are compatible with the base oil. Generally, low molecular weight, synthetic, hydrocarbon oils provide greater ease in designing and manufacturing a gel with particular desired characteristics but are more costly than less refined, high molecular weight, petroleum hydrocarbon oils. Less refined hydrocarbons may also have the disadvantage of containing sulfide compounds which can feed sulfate reducing bacteria and, in turn, tend to corrode metals such as steel, iron and iron alloys.

The carrier film or layer can have a thickness of about 1 to at least about 50 mils, and typically has a thickness of about 1 to about 1.5 mil, e.g., about 0.2 to at least 0.4 mil. Normally, the carrier is semipermeable thereby permitting anions from the surrounding environment to contact precursors to the mineralized product. By "semipermeable" it is meant to refer to a microporous structure, either natural or synthetic allowing passage of ions, water and other solvent molecules, and very small other molecules. The resin can be essentially insoluble in water and resistant to macro-penetration by flowing water. The resin layers, however, are normally permeable to water molecules and inorganic ions such as metal ions and silicate ions.

The amount of mineralized layer precursor present in the carrier typically comprises about 1 to about 60 wt. % of the carrier, e.g, normally about 5 to about 10 wt. % depending upon the carrier. The mineralized layer precursors can be combined with the carrier in any suitable conventional manner known in this art.

The mineralized layer precursors can include or be employed along with one or more additives such as the pH buffers such as those listed below in Tables A and B, mixtures thereof, among others. In some cases, a buffer also functions as a precursor, e.g., sodium silicate. The amount of these additives typically ranges from about 1 to about 60 wt. % of the carrier, e.g., normally about 5 to about 10 wt. %. These additives can be added to the carrier in order to tailor the characteristics of the mineralized layer, the carrier itself, upon a pre-treated surface, among other characteristics. By adding suitable mineralized layer precursors, carrier, additives, among other materials, the surface of the metal containing layer can be tailored by forming a mineralized layer to possess improved corrosion resistance, adhesion, among other characteristics.

                  TABLE A     ______________________________________     Examples of Buffering Compounds     Chemical Name     Formula     ______________________________________     Boric Acid        H.sub.3 BO.sub.3     Citric Acid       H.sub.3 C.sub.6 H.sub.5 O.sub.7.H.sub.2 O     Sodium Hydroxide  NaOH     Trisodium Phosphate                       Na.sub.3 PO.sub.4.12H.sub.2 O     Dodecahydrate     Potassium Silicate                       SiO.sub.2 /K.sub.2 O 1.6-2.5 wt. ratio     Sodium Silicate   SiO.sub.2 /Na.sub.2 O 2.0-3.22 wt. ratio     Potassium Hydrogen                       KHC.sub.8 O.sub.4 H.sub.4     Phthalate     Potassium Dihydrogen                       KH.sub.2 PO.sub.4     Phosphate     Borax             Na.sub.2 B.sub.4 O.sub.7     Sodium Hydrogen Carbonate                       NaHCO.sub.3     Disodium Phosphate                       Na.sub.2 HPO.sub.4.12H.sub.2 O     Dodecahydrate     Sodium Acetate    NaOOCCH.sub.3     Disodium Phosphate                       Na.sub.2 HPO.sub.4     ______________________________________

                                      TABLE B     __________________________________________________________________________     Examples of Weight Ratios of Buffering Components for Various pH Values     Desired     pH  Weight             Chemical                   Weight                       Chemical                             Weight                                   Chemical     __________________________________________________________________________     3.0 1.00             Boric Acid                   0.84                       Citric Acid                             0.18  Trisodium Phosphate     3.5 1.00             Boric Acid                   0.84                       Citric Acid                             .027  Trisodium Phosphate     4.0 1.00             Sodium                   196.00                       Potassium                             Hydrogen                                   Phthalate             Hydroxide     4.5 1.00             Sodium                   29.30                       Potassium                             Hydrogen                                   Phthalate             Hydroxide     5.0 1.00             Sodium                   11.30                       Potassium                             Hydrogen                                   Phthalate             Hydroxide     5.5 1.00             Sodium                   6.97                       Potassium                             Hydrogen                                   Phthalate             Hydroxide     6.0 1.00             Sodium                   30.40                       Potassium                             Dihydrogen                                   Phosphate             Hydroxide     6.5 1.00             Sodium                   12.20                       Potassium                             Dihydrogen                                   Phosphate             Hydroxide     7.0 1.00             Sodium                   5.84                       Potassium                             Dihydrogen                                   Phosphate             Hydroxide     7.5 1.00             Sodium                   4.14                       Potassium                             Dihydrogen                                   Phosphate             Hydroxide     8.0 1.00             Sodium                   3.64                       Potassium                             Dihydrogen                                   Phosphate             Hydroxide     8.5 1.00             Boric Acid                   0.84                       Citric Acid                             4.80  Trisodium Phosphate                                   (12 H.sub.2 O)     9.0 1.00             Boric Acid                   0.84                       Citric Acid                             5.82  Trisodium Phosphate                                   (12H.sub.2 O)     9.5 1.00             Sodium                   13.55                       Borax             Hydroxide     10.0         1.00             Sodium                   6.52                       Borax             Hydroxide     10.5         1.00             Sodium                   5.25                       Borax             Hydroxide     11.0         1.00             Sodium                   2.31                       Sodium                             Hydrogen                                   Carbonate             Hydroxide     11.5         1.00             Sodium                   8.00                       Disodium                             Acid Phosphate (12H.sub.2 O)             Hydroxide     12.0         1.00             Sodium                   1.30                       Disodium                             Acid Phosphate (12H.sub.2 O)             Hydroxide     12.5         1.00             Sodium                   15.00                       Disodium                             Acid Phosphate             Hydroxide     13.0         1.00             Sodium                   1.00                       Sodium                             Acetate             Hydroxide     __________________________________________________________________________

The aforementioned carrier can be applied to a metal containing surface by using any expedient method. Depending upon the desired results, the carrier can be applied or reapplied as appropriate. Examples of suitable methods for applying the tailored carrier comprise at least one of painting, spraying, dipping, troweling, among other conventional methods.

By employing a suitable tailored carrier, the instant invention can form a mineralized layer to protect a metal containing surface having at least one member from the group of magnesium, aluminum, vanadium, calcium, beryllium, manganese, cobalt, nickel, copper, lead, copper, brass, bronze, zirconium, thallium, chromium, zinc, alloys thereof, among others. Particularly, desirable results can be obtained when forming a mineralized layer upon a zinc containing surface.

In an aspect of the invention, the metal containing surface comprises zinc which is contacted with a carrier including sodium silicate. The carrier can comprise PAO or polyurethane. The amount of sodium silicate within a PAO carrier typically ranges from about 1 to about 30 wt. %, e.g., about 5 to about 10 wt. %, whereas for a carrier comprising polyurethane the amount of sodium silicate typically ranges from about 1 to about 15 wt. %, e.g., about 5 to about 10 with especially desirable results being obtained at about 6.5 wt. % sodium silicate. When the previously desired carrier is employed, desirable results can be obtained by applying one or more topcoats to the carrier, e.g., polyurethane, polytetrafluoroethylene, mixtures thereof, among others. The topcoat can function as a physical barrier to the surrounding environment thereby providing further corrosion resistance. The thickness of the carrier layer including any topcoat normally ranges from about 0.75 to about at least about 1.5 mils. The corrosion resistance can be further enhanced by heat treating the coated metal surface. That is, after applying a silicate containing carrier to a zinc containing surface and allowing the carrier to incubate, the coated surface is heated (in any suitable atmosphere such as air), to a temperature of about 125 to about 175° C. Consequently, the instant invention permits tailoring the carrier, mineralization precursors, topcoat as well as any heat treatment to obtain a predetermined corrosion resistance, e.g., in the case of a zinc containing surface the ASTM B117 resistance can range from 100 to 3,000 hours.

Without wishing to be bound by any theory or explanation, it is believed that the mineralized layer is formed under a variety of chemical and physical forces including 1) transporting ions through the carrier via osmotic pressure and diffusion thereby providing ions to the metal surface, 2) oxygen deprived environment, 3) buffering to provide a predetermined alkaline pH environment that is effective for formation of the mineralized layer upon a given metal surface, e.g, in the case of a zinc containing surface about 9.5 to at least about 10.5 pH, 4) heterogenious process using any available ions, 5) water present at the surface, in the carrier or as a reaction product can be removed via heat, vacuum or solvent extraction, 6) using a reservoir adjacent to the metal surface that can control that ion transport rate as well as the rate of water (and moieties) passing through the reservoir and serve to provide, as needed, a continuous supply mineralized layer precursors, among other forces.

The process for forming the inventive mineralized layer can be initiated by delivering buffering ions of combinations or single component alkali metal polyoxylates (for example sodium silicate) to passivate the metal surface, e.g., refer to item 3) in the previous paragraph. In the case of sodium silicate, the carrier contains dissolved silica in the form of a silicate anion in water as well as sodium oxide in the form of sodium hydroxide in the presence of water. If desired, sodium hydroxide can be employed maintaining the pH of the solution in a range where the silicate can remain soluble. In the case of other substrates and other anion systems, the buffering capacity of the reactants is designed to passivate the surface, manage the pH of the surface chemistry, and to prepare or condition the surface for a mineral-forming reaction. The delivery of ions is through a carrier comprising a membrane employing osmotic pressure to drive precursors to the surface.

The ionic species, which are present in the carrier or that pass through the carrier/membrane, can then interact chemically and can become associated with the surface of the metal to form a submicron mineralization layer, e.g., a monolayer. In the present invention these interactions occur adjacent to or upon the surface of the substrate to form a mineralized layer. It is to be understood that the aforementioned membrane is associated with creating an oxygenlimited passivation environment as part of the mineralization process. As a result the mineralized layer comprises an amorphous phase and a complex inorganic oxide wherein the amount of oxygen is less than stoichiometric.

Moreover, the mineralized layer precursors can interact in such a manner to produce mineralized layer in-situ at the surface. Depending upon the conditions of the surface, the substrate may contribute precursors in the form of metal ions. The metal ions of the substrate surface may exist as oxides, or the ions may have reacted with chemical species in the surrounding environment to form other metal species. In the case of a zinc substrate or surface, zinc can oxidize in the environment existing at the surface as zinc oxide, but may also form zinc carbonate from the exposure to carbon dioxide in the air. Under certain conditions, the zinc carbonate will predominate the surface species of the precursor to form the mineralized surface. In the case of other metal substrates, the ability of the surface to contribute ions to function as mineral precursors can be achieved by conditioning the surface, e.g., to populate the surface with oxide species that will participate as mineralized layer precursors. Examples of surface preparation or surface conditioning include employing an anodic or oxidizing agent such as peroxide or sodium bicarbonate, mixtures of agents, among others.

Depending upon the carrier and process condition, precursors can pass through the carrier membrane system as anions, and interact adjacent to or upon the surface with metal cations, which in most cases are donated by the metal surface or substrate to form a relatively thin mineralized layer, e.g., a monolayer. In one aspect of the invention, sodium silicate (as SiO3-ion) reacts with a zinc containing surface, e.g., that exists primarily as zinc carbonate, to form an amorphous mineralization layer containing a nanocrystaline hemimorphite phase that is normally less than 100 Angstroms in thickness. In this aspect of the invention, the metal surface was prepared for mineralization by the presence of a suitable buffering alkali, e.g., buffering with a silicate to a pH in the range of about 9.5 to about 10.5. While a higher pH can be effectively used, a pH of less than about 11 minimizes the need for certain relatively complex and expensive handling procedures.

In another aspect of the invention, the delivery of pH buffering agents as well as the anion reactants can be designed to tailor the surface characteristic. For example, in order to achieve improved resistance to acid rain on a zinc surface, the silicate anions can be complemented with zirconate anions. Further, in the case of an iron containing surface, the carrier can deliver silicate anions to a anodically conditioned surface to form amorphous phase comprising julgoldite.

While any suitable buffer can be employed for practicing the invention, buffer solutions are typically prepared by mixing a weak acid and its salt or a weak base and its salt. Acidic buffers, for example, can be prepared using potassium chloride or potassium hydrogen phthalate with hydrochloric acid of appropriate concentrations. Neutral buffers can be prepared by mixing potassium dihydrogen phosphate and sodium hydroxide, for example. Alkaline (basic) buffers can be prepared by mixing borax or disodium hydrogen phosphate with sodium hydroxide, for example. Many more chemical combinations are possible, using appropriate chemicals to establish the proper sequence of proton transfer steps coupled with the intended reactions. Buffer exchange rates may be modified by combinations of buffer materials that react at different ionic exchange rates; buffers of low-change type react more rapidly than high-change types.

Aqueous polymers are preferred carriers for buffers in liquid form and include water-reducible alkyds and modified alkyds, acrylic latexes, acrylic epoxy hybrids, water reducible epoxies, polyurethane dispersions, vinyls and ethylene vinyl acetates, and mixtures thereof. Such polymers are water vapor permeable but are repellent of liquid water and are essentially water insoluble after curing. These polymers can form a semipermeable membrane for water vapor and ionic transfer. Hence, if the surface of the metal substrate is dry, water vapor can permeate the membrane; but, buffering ions, which are present in the membrane or that pass through the membrane, can passivate the metal surface thereby reducing corrosion.

Buffer materials are chosen based on the type of the surface or substrate to be protected. Metal substrates may be protected from corrosion by passivating the substrate surface. Such passivation may generally be accomplished only in certain pH ranges which, in turn, depend on the specific substrate to be protected. For example, iron based alloys are passivated with an alkaline pH (pH 8-12). This pH range is preferably accomplished with sodium silicate and/or potassium silicate powders; but other alkaline materials may be used. A blend of sodium and potassium silicates is also useful for achieving viscosity control in aqueous carrier/membrane formulations.

In a further aspect of the invention, a mineralized layer is obtained by mixing silicates and anodic oxidizing materials such as sodium carbonate and delivering the mixture in a manner effective to activate the metal surface.

While the above description emphasizes a zinc containing surface, the surface of a wide range of metal surfaces can be altered to impart beneficial surface characteristics. In most cases, the substrate or the surface thereof contributes cations to the mineralization-forming reaction. Examples of metal surfaces include zinc, iron, copper, brass, iron, steel, stainless steel, lead, alloys thereof, among others. In the case of limited mineral layer formation or thickness of the mineral layer is caused by the surface contribution of the cation, an improved result can be obtained by managing or tailoring the pH. That is, the buffering capacity and the pH of the carrier is substrate surface-specific and is tailored to manage the surface chemistry to form the inventive mineralization layer, e.g., selecting a pH at which the surface is reactive encourages formation of the mineralization layer. The reaction for forming the new surface with continue until such time that the finite quantity of metal atoms at the surface are consumed. If the new mineralized layer is marred or destroyed, a desirable aspect of the instant invention is that the surface will reinitiate mineralization formation with any available precursors. The ability to reinitiate mineralization or self-repair damaged surfaces is a novel and particuraly desirable characteristic of the invention.

The delivery/method of the alkali metal polyoxolates (or mineralization layer) can be provided through a membrane from a reservoir as described in the U.S. patent application Ser. No. 08/634,215; previously incorporated by reference. In the present invention, soluble precursors, such as silicate materials, are used within one or more coating layers. For example, in a polymer containing carrier system, one of the layers would be charged with sodium or potassium silicates wherein the outer layer(s) are employed to control the rate of moisture flow through the carrier. These carriers are typically relatively hard films as the normal polymerization of the carrier occurs to form a plastic type polymer type coating. Additional delivery methods have been developed utilizing soft films, gels, sealants, adhesives, and paints wherein the membrane feature is formed in-situ by the reaction between a silicate, e.g., sodium silicate, and silica. By controlling the quantity of the silica in the carrier, the mineralized layer can be designed to suit the specific application. Depending upon the pH and relative concentration of silicate and silica, the degree of crystal formation, e.g., a silica containing hemimorphite within an amorphous layer, can also be designed to achieve a predetermined result.

Without wishing to be bound by any theory or explanation the formation of the mineralized layer can occur under a wide range of conditions (normally ambient) and via a plurality of mechanisms. Normally, the mineralization layer forms underneath the carrier upon the metal surface, e.g., as buried layer under a carrier comprising a reservoir of precursors. If so formed, whatever ions are needed in the reservoir layer to form the mineralized layer, are expediently included as water soluble salts in the reservoir layer. On the other hand, all the ions employed to form the mineralized layer need not necessarily be included in the reservoir layer. That is, if desired cations can be supplied from the underlying metal surface and need not necessarily be included as water soluble salts in the reservoir layer. Such cations can be obtained from the surface of the substrate metal itself, by reaction of the substrate with the anions of the precursor component for the mineralized layer. Since the mineralized layer is normally relatively thin, sufficient cations for the mineralized layer can even be supplied from the substrate when present only as an alloying ingredient, or perhaps even as an impurity. Additionally, the cations needed for the mineralized layer can be supplied from water soluble salts in the reservoir layer, as indicated above. Further, if the mineralized layer is to be formed from an overlying reservoir layer that also contains buffer components, at least some to the salts used for buffering can be employed for forming the mineralized layer. The latter reservoir layer would possess a self healing effect by functioning as a source of minerization precursors in the event the layer was damaged. Once the mineralization layer has been formed to the degree desired, the carrier or reservoir layer can remain as a component of the finished article or removed.

Applications for the films and coatings of the invention include, for example, components such as coatings and paints of components, parts and panels for use the automotive industry, home-consumer products, construction and infrastructures, aerospace industry, and other out-door or corrosive applications wherein it is desirable to improve the characteristics of a metal surface and the use of heavy metals in elemental or non-elemental form is environmentally undesirable. The films and coatings may be applied to new products or over conventional platings to extend the useful service life of the plated component.

While the above description places particular emphasis upon forming a silicate containing mineralized layer, one or more mineralized layers having chemically similar or distinct compositions can be applied upon the same metal surface. If desired, the mineralized surface can be further modified by using conventional physical or chemical treatment methods.

The following Examples are provided to illustrate not limit the scope of the invention as defined in the appended claims. These Examples contain results of the following analysis: Auger Electron Spectroscopy (AES), Electronic Impedance Spectroscopy (EIS), and X-ray Photoelectron Spectroscopy (XPS). These analysis were performed using conventional testing procedures. The results of the AES demonstrate that the thickness of the mineralized layer can range from about 10 to 50 microns. EIS demonstrates that the mineralized layer imparts corrosion resistant properties to the surface, e.g., a reduced Icorr corresponds to a reduced corrosion current and in turn a reduced corrosion rate. The XPS data demonstrates the presence of a unique hemimorphite crystal within the mineralized layer, e.g., XPS measures the bond energy between silicon and oxygen atoms and compares the measured energy to standardized values in order to determine whether or not known crystals are present. Conventional X-ray diffraction analysis confirmed that the mineralized layer is predominately amorphous, e.g., an X-ray measurement resulted in wide bands thereby indicating the presence of an amorphous phase.

EXAMPLES Auger Electron Spectroscopy

Examples 1-4 were prepared and analyzed in accordance with the following AES procedure.

    ______________________________________     Instrumentation Used     ______________________________________     Instrument:     Physical Electronics 545, Single Pass                     Cylindrical Analyzer     Sample Excitation:                     Electron Gun                     Emission Current, 1 mA                     Beam Voltage, 3 kV     Electron Beam Detection:                     Multiplier Voltage, 1 kV                     Modulation Voltage, 3 eV     Signal Detection:                     Lock-in Magnification, 10X                     Lock-in Time Constant, 0.001 sec.     Sputter Gun Settings:                     Beam Voltage, 3 kV                     Focus Dial Setting, 2                     Raster X Dial Setting, 10                     Raster Y Dial Setting, 10                     Emission Current, 15, mA                     Sputter Rate, 12 A/min                     Start Time, 0 min.                     Final Time, 30 min                     Sputter Depth, 360 A     ______________________________________

Example 1

The coating had a first layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60° C. for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60° C. for 10 minutes. The second layer was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual coating was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 2

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60° C. for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60° C. for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual coating was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 3

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard zinc phosphated, 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60° C. for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60° C. for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 4

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard iron phosphated, 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60° C. for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60° C. for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Each of the previously described washed test panels were passed through an AES analysis in accordance with conventional methods. This analysis confirmed the presence of the inventive mineral layer and generated data which demonstrated that for each substrate, the thickness of the mineralized layer was on the order of about 50 to about 70 Å thick.

Electrical Impedance Spectroscopy

Examples 5 through 13 were prepared for Electrochemical Impedance Spectroscopy (EIS) analysis. EIS is one method of determining corrosion rates of a metal or a coated metal. In this technique, a small-amplitude sinusoidal potential perturbation was applied to the working electrode at a number of discrete frequencies ranging from 60,000 Hz to 0.0005 Hz. At each one of these frequencies, the resulting current waveform exhibited a sinusoidal response that was out of phase with the applied potential signal by a certain amount. The electrochemical impedance was a frequency-dependent proportionality factor that acts as a transfer function by establishing a relationship between the excitation voltage signal and the current response of the system. This method was detailed by the American Society for Testing and Materials (ASTM) in Electrochemical Corrosion Testing, STP 727.

Example 5

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

90% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual gel was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 6

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% G-Grade Sodium Silicate (PQ Corporation)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 7

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% Sodium Molybdate (Fisher Scientific)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 8

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% Sodium Phosphate (Fisher Scientific)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

This Example was repeated with the exception that sodium carbonate was employed instead of sodium phosphate.

Example 9

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 10

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 11

A coating was prepared having the following formulation (by weight):

6.5% Sodium Vanadate Solution (156.3 grams/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 12

A coating was prepared having the following formulation (by weight):

6.5% Sodium Molybdate Solution (274.21 grams/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each coat was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 13

A coating was prepared having the following formulation (by weight):

6.5% Sodium Carbonate Solution (120.12 grams/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

The cleaned samples from Examples 5 to 13 were then tested by EIS in accordance with the following method.

    ______________________________________     Instrument:                Solartron 1287 Electrochemical Interface                Solartron 1260 Impedance/Gain-Phase Analyzer                ZWare and CorrWarr Software by Scribner     Settings:  60,000 to .005 Hz.                10 steps/decade                5 mV rms AC signal     ______________________________________

Test Solution: 1Molar Ammonium Sulfate, pH=3.0 (using 0.1N Sulfuric Acid) for electrogalvanized substrates.

1Molar Ammonium Sulfate, pH=2.0 (using 0.1N Sulfuric Acid) for 1010 Steel substrates.

B value: corresponds to the average of the Tafel slope B=(BcBa)/(Bc+Ba) icorr: corresponds to the current generated by corrosion.

The following Table sets forth the results of the EIS Procedure for the zinc substrate in Examples 5-8.

    ______________________________________     EIS TABLE FOR ZINC SUBSTRATES                     i.sub.corr      ave. i.sub.corr                                           EXPL  Com-     surface            B        μA/cm.sup.2                              ave. B μA/cm.sup.2                                           NO.   ments     ______________________________________     Bare Zinc            0.062632 193.3    0.067255                                     205.5 standard            0.060229 204.4                 std            0.063586 226.3                 std            0.101038 85.3                  std   .sup.1            0.071548 213.1                 std            0.0792307                     243.6                 std   .sup.11            0.078282 190.2                 std     Gel    0.054997 120.4    0.055658                                     130.1 5            0.045513 148.5                 5            0.035642 64.8                  5            0.041034 79.7                  5            0.039146 72.5                  5            0.060190 113.1                 5            0.061932 138.5                 5     Na.sub.2 SiO.sub.4            0.072070 110.7    0.047529                                     97.5  6            0.059899 121.5                 6            0.035932 93.2                  6            0.038235 107.7                 6            0.040076 67.3                  6            0.038964 84.7                  6     ______________________________________      .sup.1 Cell leaked at the base, setting up a localized galvanic cell.      .sup.1 Cell leaked underneath gasket.     ZINC EIS TABLE CONTINUED            B        i.sub.corr                              ave. B ave. i.sub.corr                                           EXMPL Com-     surface            (mV)     μA/cm.sup.2                              (mV)   μA/cm.sup.2                                           NO    ments     ______________________________________     Na.sub.2 MoO.sub.4            0.052667 99.3     0.061923                                     128.5 7            0.072482 191.1                 7            0.059900 98.5                  7            0.065942 128.6                 7            0.058622 125.0                 7            0.090991 153.9                 7     .sup.2     Na.sub.2 PO.sub.4            0.047173 93.3     0.049479                                     153.9 8            0.045828 141.0                 8            0.053326 232.8                 8            0.056754 178.1                 8            0.058574 194.0                 8            0.035220 84.2                  8     Na.sub.2 CO.sub.3            0.041397 68.4     0.047339                                     98.7  8            0.044320 121.8                 8     .sup.2            0.046295 81.1                  8            0.057343 123.4                 8     .sup.2     ______________________________________      .sup.2 Cell leaked at the base, discarded this data point.

The results of the EIS indicates that the greatest corrosion resistance (low icorr) for a zinc substrate is obtained by a sodium silicate or sodium carbonate mineral layers.

The following Tables list the corrosion data for the steel surfaces of Examples 9-13.

    ______________________________________               Hours     B       R.sub.p                                        i.sub.corr     surface   Immersed  (mV)    (ohm-cm.sup.2)                                        (μA/cm.sup.2)     ______________________________________     Coating Without Silicates-Example 9     steel     24        39.4    68     580     --        49        33.8    55     614     --        74        33.8    116    290, pH = 2.86     --        99        33.8    25     1352, pH = 2.0     --        21        34.4    54     637     --        44        36.3    95.8   379     --        68        45      55.6   808, pH = 2.36     --        1         46.1    59.3   777     --        24        41.7    43.8   952     --        48        43.3    55.5   780, pH = 2.4     --        1         42      135    311     --        24.5      40.8    51.8   788     --        48        40.5    53     764, pH = 2.5     Coating Containing Sodium Silicate-Example 10     steel     24        30.3    47.5   640     --        49        35.3    55     642     --        74        35.3    267    132, pH = 3.15     --        99        35.3    20     1765, pH = 2     --        1.5       43.4    74.4   584     --        21        35.5    94.2   377     --        44        31.5    125    252     --        68        33.8    172    196, pH = 2.25     steel - coating               1         36.7    564     65     was not     completely     stripped     steel     26        33.2    371     90     --        57        33.2    554     60     steel - coating               1         42.4    32.6   1300     was restripped     steel     1         42.2    59.7   707     --        24        40.8    58.7   695     --        48        40.8    70.2   581, pH = 2     Coating Containing Sodium Vanadate-Example 11     steel     25        305.8   55.5   645     --        49        33.9    75.8   448     --        74        33.9    82.6   410, pH = 2.8     --        78        42.2    25.7   1640, pH = 2     --        1.5       50.5    70     721     --        21        36.5    92     397     --        44        33.3    126    265     --        68        33.2    161    206, pH = 2.25     --        1         40.8    146    280     --        24        40.6    64.6   632     --        48        40.6    75.6   537, pH = 2     --        1         42.6    62.9   677     --        24        34.6    65     536     --        48        39.1    110    355, pH = 2.1     Coating Containing Sodium Molybdate-Example 12     steel     21        37.4    51.3   729     --        44        44.4    45.6   973     --        68        41.4    54.3   763, pH = 2.35     steel - coating               1         37.7    190    198     was not     completely     removed     steel     26        36.6    138    265     --        57        36.6    212    173     steel - coating               1         33.3    112    353     was not     completely     removed)     --        24        40.4    96.6   409     --        48        39.5    130    293, pH = 2.2     --        1         46.9    42.5   1109     --        24        48.2    28.6   1687     --        44        46      45.2   1018, pH = 2.15     Coating Containing Sodium Carbonate-Example 13     steel     25        37.2    82.5   451     --        49        27.6    123.5  223     --        74        27.6    128.8  214, pH = 2.3     --        78        37.2    34.4   1080, pH = 2     --        1         41.8    56.8   735     --        24.5      44.2    33.5   1320     --        48        43.4    40.7   1066, pH = 2.9     --        1         39.5    112    353     --        24        40.6    96.6   409     --        48        38.1    130    293, pH = 2.2     --        1         45.7    46.7   978     --        24        46.5    29.7   1566     --        44        44.4    41.4   1072 pH = 2.15     ______________________________________

Based upon the measured corrosion currents, sodium carbonate and sodium silicate are the most effective in reducing the icorr thereby indicating a reduced corrosion rate.

X-Ray Photoelectron Spectroscopy (XPS)

X-ray Photoelectron Spectroscopy (XPS) was performed on a series of samples in Examples 14-24 that included 1010 Steel and Electrogalvanized Steel. XPS was performed in accordance with conventional procedures in this art.

    ______________________________________     Instrumentation Used     ______________________________________     Instrument:      Physical Electronics 5701 LSci     X-ray Source:    Monochromatic aluminum     Source Power:    350 watts     Analysis Region: 2 mm × 0.8 mm     Exit angle:      65°     Acceptance angle:                      ±7°     Charge reference:                      B.E. of C-)H,C) = 284.6 eV     Charge neutralization:                      flood gun     Sampling Depth:  (3λ) was 70 A     ______________________________________

Example 14

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 15

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 1 hour at 125° C., using a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 16

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 17

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 18

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 125° C. for one hour, in a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 19

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60° C. for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 175° C. for one hour, in a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 20

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Sodium Silicate

The sample panel was allowed to air dry.

Example 21

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Sodium Silicate

The sample panel was allowed to air dry. The panel was then exposed to a post-dry heat treatment of 125° C. for one hour, in a standard laboratory oven.

Example 22

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Sodium Silicate

The sample panel was allowed to air dry. The panel was then exposed to a post-dry heat treatment of 175° C. for one hour, in a standard laboratory oven.

Example 23

A crystal sample of Zn₂ SiO₄, which was air fractured and immediately introduced into the sample chamber of the XPS. The total air exposure was less than 2 minutes. The surface was examined initially with a low resolution survey scan to determine which elements were present. High resolution XPS spectra were taken to determine the binding energy of the elements detected in the survey scan. The quantification of the elements was accomplished by using the atomic sensitivity factors for a Physical Electronics 5701 LSci ESCA spectrometer.

The following Table sets forth the silicon binding energies which were measured for Examples 14-23.

    ______________________________________     Example Number                 Treatment   Si 2p peak Energy (eV)     ______________________________________     14          Room Temp   101.9     15          125° C.                             101.8     16          Room Temp   102.8     17          Room Temp   102.8     18          125° C.                             102.6     19          175° C.                             102.6     20          25 ppm Na.sub.2 SiO.sub.4,                             101.7                 25° C.     21          25 ppm Na.sub.2 SiO.sub.4,                             101.7                 125° C.     22          25 ppm Na.sub.2 SiO.sub.4,                             101.8                 175° C.     23          Zn.sub.2 SiO.sub.4 crystal                             101.5     ______________________________________

The above Table illustrates that there has been a change in the concentration of Si as well as the bond energy thereby providing further confirmation of the presence of the mineralized layer. Further, the Si--O bond energy of conventional zinc silicate crystal as well as the silicate soaked panels is distinct from the inventive mineralized layer.

Example 24

A coating was prepared having the following formulation (by weight):

6.5% N-grade sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The formulation above was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three coats. Each coat was dried to tack free at 60° C. for 15minutes. The panel was exposed to ASTM B117 Salt Fog Chamber for 2400 hours. At the end of the salt fog exposure, there were large areas of the panel that were uncorroded. The area of uncorroded surface was cut into a small square sample and the urethane coating was removed by hand, using small tweezers. The sample was analyzed in accordance with the previously identified XPS method on an instrument of comparable sensitivity and accuracy. The results of the XPS are set forth in the following Table.

    ______________________________________     Example 24 Silicate Containing Coating Followed by Salt Spray Exposure                                      Relative                                      Concentration of                                      Silicon on     Example                Si 2p peak                                      the Surface     Number Treatment       Energy (eV)                                      (% wt)     ______________________________________     14     urethane coating, room                            101.9     negligible at 1.0%            temp     15     urethane coating,                            101.8     negligible at 0.8%            125° C.     16     silicate, room temp                            102.8     19.8%     17     silicate        102.8     18.9%            125° C.     18     silicate,       102.6     15.8%            room temp     19     silicate,       102.6     11.6%            175° C. (heat applied after            coating removed)     20     immersion,      101.7     4.1%            25 ppm Na.sub.2 SiO.sub.4,            25° C.     21     immersion,      101.7     3.2%            25 ppm Na.sub.2 SiO.sub.4,            125° C.     22     immersion,      101.8     3.9%            25 ppm Na.sub.2 SiO.sub.4,            175° C.     23     Zn.sub.2 SiO.sub.4 crystal                            101.5     NA     24     silicate, room temp, 2400                            102.6     8.1%            hours of B117 exposure     ______________________________________

The above Table illustrates that the binding energy for the surface exposed to the silicate containing coatings range from 102.6 to 102.8. By observation of the XPS peak, it was observed that these energy values were actually manifold values from manifold peaks that contain more than one material. These materials can be characterized as a disilicate, or hemimorphite (bonding energy at 102.2), altered by the presence of Si--O bonds, as in SiO2 (bonding energy at 103.3) and Si--O--C bonds with a bonding energy of 103.6 or 103.7. Such a bonding energy and concentration of Si on the surface are distinct from conventional silica or silicate structures. The binding energy, for zinc silicate, Zn₂ SiO₄, 101.5 eV, is also distinct from the binding energy of the mineralized layer, 102.7 eV, or the hemimorphite.

Example 25

The corrosion resistance of the following formulations were evaluated by salt spray testing per ASTM-B117 specifications with the panels positioned with the 6 inch long edge at the top and the bottom to preclude each of the test areas on each panel from affecting the adjacent area.

The coating formulations were prepared as follows:

1. Formula #1: was prepared by adding 781 g. water to 2342 g. NeoRez R9637 polyurethane dispersion (Zeneca Resins) to achieve a composition of 75% by weight R9637 and 25% by weight water. The viscosity of the composition was 35 cP Brookfield (#2 spindle, speed 20, 70° F.).

2. Formula #2: was prepared by diluting 143.5 mL N grade sodium silicate solution (PQ Corporation) with 345 mL distilled water and slowly mixing this into 2134.5 grams of NeoRez R9637 resin while stirring with an air powered Jiffy Mixer for approximately 15 minutes. The viscosity of the composition was 38 cP Brookfield (#2 spindle, speed 20, 70° F.) and had a pH of 10.5 (pH paper).

The coatings formulations were used to coat electrogalvanized steel panels and hot-dipped galvanized zinc panels. The electrogalvanized panels were supplied by ACT (ACT E60 EZG 60G) 2 side, clean, unpolished. The hot-dipped galvanized panels were obtained-from a metal building supplier (Bulter) and cut to size specifications. Each coating layer was applied with a #12 Jr. Drawdown rod to produce a 1.2 mil wet film coating thickness. Each coating layer was dried to a tack free condition by baking in a forced air convection oven at 60° C. for 15 minutes before subsequent coating layers were applied. The overall dry film coating thickness on all of the panels averaged 1.4 mils.

Sample 1:

Sample Name: Egalv. Control Sample

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolish zinc coated panel.

Coating: None (control sample)

Additional Treatments: None

Sample 2:

Sample Name: Hot-dipped Control Sample

Substrate: HotDipped Zinc Panel 03X06X075

Coating: None

Additional Treatments: None

Sample 3:

Sample Name: Urethane Control Sample

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 3 coats of Formula #1

Additional Treatments: None

Sample 4:

Sample Name: Heated Urethane Control Sample

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 3 coats of Formula #1

Additional Treatments: 75° C. for 1 hour

Sample 5:

Sample Name: Single Formula #2 Coat

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 1 coat of Formula #2

Additional Treatments: None

Sample 6:

Sample Name: Single Formula #2+Topcoat

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 1 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: None

Sample 7:

Sample Name: 2-layers of Formula #2

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, uhpolished zinc coated panel.

Coating: 2 coats of Formula #2

Additional Treatments: None

Sample 8:

Sample Name: Single layer of Formula #2+Topcoat

Substrate: HotDipped Zinc Panel

Coating: 1 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: None

Sample 9:

Sample Name: 3-layer Formula #2

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolish zinc coated panel.

Coating: 3 coats of Formula #2

Additional Treatments: None

Sample 10:

Sample Name: 3-layers of Formula #2

Substrate: HotDipped Zinc Panel.

Coating: 3 coats of Formula #2

Additional Treatments: None

Sample 11:

Sample Name: 2 layers of Formula #2+Topcoat

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 2 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: None

Sample 12:

Sample Name: 2 layers of Formula #2+Topcoat

Substrate: HotDipped Zinc Panel.

Coating: 2 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: None

Sample 13:

Sample Name: 2 layers of Formula #2+Topcoat+Heat

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolish zinc coated panel.

Coating: 2 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: 75° C. for 1 hour

Sample 14:

Sample Name: 2 layers of Formula #2+Topcoat+Heat

Substrate: ACT E60 EZG 60G 2 Side E-Galv., clean, unpolished zinc coated panel.

Coating: 2 coat of Formula #2, than 1 coat of Formula #1

Additional Treatments: 175° C. for 1 hour

The results of analyizing the above Samples in accordance with ASTM B117.

    ______________________________________                         Performance Hours                         ASTM B117     Sample                             5% Red     No.      Substrate        1st Red  Rust     ______________________________________     1        Zinc Egalv Control                               24       120     2        Zinc Hot-dipped Control                               24       528     3        Urethane Control 320      452     4        Heated Urethane Control                               384      672     5        Single Layer     864      1080     6        Single Layer + Topcoat                               876      1100     7        2-Layer          1288     1476     8        Single Layer + Topcoat                               1308     1500     9        3-Layer          1206     1320     10       3-Layer          1200     1300     11       2-Layer + Topcoat                               1336     1608     12       2-Layer + Topcoat                               2000     2400     13       2-Layer + Topcoat + Heat                                2300+    2600+     14       2-Layer + Topcoat + Heat                                2500+    3000+     ______________________________________

The above Table illustrates that the instant invention can be employed for increasing the corrosion resistance of a zinc containing surface by a factor of at least 8, e.g, compare samples 4 and 14.

Example 26

This Example illustrates whether or not corrosion resistance is imparted by an alkaline pH (attributed to Sodium Hydroxide) and whether the presence of the soluble silicate ion offers any additional protection beyond the contribution of the alkaline pH.

This Example was performed by preparing and testing three sets of formulations:

1. 3 layers of polymer with no additives.

2. 3 layers of water-borne polymer with a pH adjusted to that of a alkali silicate doped coating.

3. 3 layers of polymer with sodium silicate added.

The coating formulations were prepared as follows:

1. The coating for formulation 1. was prepared by adding 781 g. water to 2342 g. NeoRez R9637 polyurethane dispersion (Zeneca Resins) to achieve a composition of 75% by weight R9637 and 25% by weight water. The viscosity of the composition was 35 cP Brookfield (#2 spindle, speed 20, 70° F.).

2. The coating for formulation 2. was prepared by dissolving 2.4335 g. NaOH (sodium hydroxide powder) in 41.2 G. of distilled water. This sodium hydroxide solution was slowly mixed into 254 g. NeoRez R9637 resin with an air powered Jiffy Mixer over the course of 5 minutes. The viscosity of the composition was 60 cP Brookfield (#2 spindle, speed 20, 70° F.) and had a pH of 10.5 (pH paper).

3. The coating for formulation 3. was prepared by diluting 143.5 mL N grade sodium silicate solution (PQ Corporation) with 345 mL distilled water and slowly mixing this into 2134.5 grams of NeoRez R9637 resin while stirring with an air powered Jiffy Mixer for approximately 15 minutes. The viscosity of the composition was 38 cP Brookfield (#2 spindle, speed 20, 70° F.) and had a pH of 10.5 (pH paper).

The coating formulations were used to coat electrogalvanized steel panels. The electrogalvanized panels were ACT E60 EZG 60G 2 side, clean, unpolished from APR 29396 Batch 30718614. Each coating layer was applied with a #12 Jr. Drawdown rod to produce a 1.2 mil wet film coating thickness. Each coating layer was dried to a tack free condition by baking in a forced air convection oven at 60° C. for 15 minutes before subsequent coating layers were applied. The overall dry film coating thickness on all of the panels averaged 1.4 mils. The following panels were prepared:

    ______________________________________             First      Second  Third     surface Layer      Layer   Layer    alkali     ______________________________________     Egalv   Formula    Formula Formula  PANTST27             #1         #1      #1     Egalv   Formula    Formula Formula  ConNaOH             #3         #3      #3     Egalv   Formula    Formula Formula  Zn--NaOH             #2         #2      #2     ______________________________________

Five panels each having the surface and layering shown in the above Table were subjected to ASTM-B117 salt spray exposure until all panels in the group developed red corrosion on 5% of its surface, or approximately 1500 hours of test exposure was achieved. The average time in test hours to the development of first red corrosion and to development of red corrosion on 5% of each sample surface(Failure) is shown in the Table below:

AVERAGE SALT SPRAY RESULTS FOR ELECTROGALVANIZED STEEL PANELS

    ______________________________________                     Avg                     Hours     Coating         First    Avg Hours 5%     Formulation     Red      Red (Fail)     ______________________________________     Polyurethane Only                     308      448     Polyurethane pH 456      616     Adjusted     Polyurethane + Na                     1176*     1336**     Silicate     ______________________________________      *Two test panels did not develop red corrosion during the ASTM B117 Test.      **Two test panels did not develop red corrosion during the ASTM B117 Test

The above two Tables illustrate that when applied over electrogalvanized steel panels, polyurethane coatings which contain sodium silicate perform a minimum of three times better than the polyurethane coating by itself, whereas only a 1.5 times improvement can be obtained by adjusting the polyurethane coating pH to 10.5. The presence of the sodium silicate imparts a corrosion resistance benefit significantly greater than that arising from the alkaline pH.

Example 27

The purpose of this Example is to determine the effect on corrosion resistance of adding different loadings of G grade sodium silicate powder (PQ Corporation) to a urethane carrier.

The 1,5,10,15,20,25,30 wt. % sodium silicate batches were prepared by adding 2,10,20,30,40,50, and 60 grams, respectively, of G grade sodium silicate powder(PQ Corporation) to 200 grams of PAO Grease(AM940126 supplied by Nye Lubricants Inc.) and mixing by hand for approximately 30 minutes.

The mixed silicate containing grease was evaluated by applying the grease upon ACT E60 EZG 60G 2 Side E-Galv., clean, unpolish zinc coated panels. The grease was applied to the panels by applying an excess to the panels and running a gate type applicator across the panels to leave behind a 1/16 inch thick gel coating. Two panels were coated per substrate/grease loading.

Prior to testing, the grease was removed from the bottom 3-3.5 inches of the panels by lightly scraping the excess off with manilla tags, leaving a thin film of gel on the surface. The base oil of the gel was then removed from this thin film by soaking and rinsing with naphtha. The cleaned surface of the panels appeared to be covered with a thin white deposit postulated to be silica and sodium silicate. Each test panel consisted of an uncoated area approximately 1 inch wide at the hole end of the panel followed by a 1.5-2 inch width containing unremoved gel and finally containing a 3-3.5 inch wide area where the gel had been removed.

The panels were evaluated by salt spray testing per ASTM-B117 specifications with the panels positioned with the 6 inch long edge at the top and the bottom to preclude each of the test areas on each panel from affecting the adjacent area.

    ______________________________________                Salt Spray Hours (ASTM B117)     Wt %     test                      Average     silica   basis   Panel 1     Panel 2                                        hours     ______________________________________     0        First   480         672   576              Red              5% Red  648         1224  936     1        First   504         816   660              Red              5% Red  792         1248  1020     5        First   1296        1320  1308              Red              5% Red  2064        1872  1968     10       First   1320        1368  1344              Red              5% Red  1584        1536  1560     15       First   1176        1176  1176              Red              5% Red  1416        1536  1476     20       First   768         1200  984              Red              5% Red  1080        1416  1248     25       First   1152        1200  1176              Red              5% Red  1416        1416  1416     30       First   1152        1200  1176              Red              5% Red  1320        1416  1368     ______________________________________

The corrosion resistance of zinc coated panels was affected by the amount of silicate in the carrier. The above Table demonstrates that the presence of at least 1% sodium silicate significantly enhances the corrosion performance.

It is to be understood that the foregoing is illustrative only and that other means and techniques may be employed without departing from the spirit or scope of the invention as defined in the following claims. 

The following is claimed:
 1. An amorphous mineralized surface which comprises a metal substrate selected from the group consisting of zinc and a zinc containing alloy, and a mineralized layer comprising an inorganic oxide in a crystalline phase and an amorphous phase said inorganic oxide having the formula Zn_(x) M'_(y) M"_(z) (SiO₄)_(t) (Si₂ O₇)_(u) (OH)₂.nH₂ O where M' and M" each comprise a cation selected from the group coilsisting of Group I, II and III metals, and wherein x, y and z each can be any number including zero provided that x, y and z are not all concurrently zero; and t and u each can be any number including zero provided that t and u are not both concurrently zero.
 2. An amorphous mineralized surface comprising a metal substrate selected from the group consisting of zinc and a zinc containing alloy, and a mineralized layer comprising a crystalline inorganic oxide and an amorphous phase, said crystalline inorganic oxide comprising sodium, zinc, silicon and oxygen.
 3. An amorphous mineralized surface comprising a metal substrate selected from the group consisting of zinc and a zinc containing alloy, and a mineralized layer comprising a complex inorganic oxide and an amorphous phase, said complex inorganic oxide comprising an alkali metal, zinc, silicon and oxygen.
 4. An amorphous mineralized surface formed by applying a mineral precursor comprising at least one carrier aid at least one alkali metal silicate onto a surface comprising zinc or a zinc containing alloy thereby forming a mineralized layer comprising a crystalline inorganic oxide and an amorphous phase, said crystalline inorganic phase comprising an alkali metal, zinc, silicon and oxygen.
 5. A corrosion resistant amorphous mineralized surface formed by reacting a surface comprising zinc or a zinc containing alloy with a mineral precursor comprising at least one alkali metal silicate thereby forming a mineralized layer comprising a complex inorganic oxide and an amorphous phase, said complex inorganic oxide comprising an alkali metal zinc, silicon and oxygen.
 6. The amorphous mineralized surface of claim 1 wherein either M' or M" is an alkaline metal.
 7. The amorphous mineralized surface of any one of claims 1, 2, 3, 4, or 5 wherein the XPS value of the silicon binding energy is from about 102.6 to about 102.8 eV.
 8. The amorphous mineralized surface of any one of claims 1, 2, 3, 4, or 5 having an ASTM-B117 corrosion resistance of from 100 hours to 3,000 hours.
 9. The amorphous mineralized surface of claim 6 wherein the alkaline metal is sodium.
 10. The amorphous mineralized surface of any one of claims 1, 2, 3, 4, or 5 wherein the amount of oxygen is less than stoichometric inorganic oxide.
 11. The amorphous mineralized surface of any one of claims 1, 2, 3, 4, or 5 wherein the mineralized layer has a thickness of at least about 50 Angstroms.
 12. The amorphous mineralized surface of any one of claims 3, 4, or 5 wherein the alkali metal comprises at least one of sodium, calcium and potassium.
 13. The amorphous mineralized surface of any one of claims 3, 4, or 5 wherein the inorganic oxide comprises a hydrated hemimorphite comprising sodium, zinc, silicon and oxygen.
 14. The amorphous mineralized surface of claim 12 wherein the alkali metal comprises calcium.
 15. The amorphous mincralized surface of claim 5 wherein the alkali metal silicate comprises at least one member selected from the group consisting of sodium silicate, calcium silicate and potassium silicates. 